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She was chosen as a bride for the Tsar by his mother Natalia Naryshkina primarily on account of Eudoxia's mother's relation to the famous boyarFyodor Rtishchev. She was crowned Tsarina in 1689 and gave birth to Grand Duke Alexei Petrovich of Russia the following year. She would have two more sons by Peter, Alexander in 1692 and Paul in 1693, but both died during infancy. The Tsar could not stand her conservative relatives and soon abandoned her for a German beauty, Anna Mons. Eudoxia's letters to Peter were full of complaints and exhortations of unrequited love.

In 1696, during his prolonged journey to Western Europe, Peter asked his Naryshkin relatives to persuade Eudoxia to enter a monastery. This could not be effected until 1698, when she was finally banished to the Intercession Convent of Suzdal. The local hegumen, however, allowed her to live there much as a lay woman would. She even found herself a lover, an officer named Stepan Glebov, who later would be executed by quartering.

Gradually, Eudoxia and her son became the centre of opposition to Peter's reforms, primarily from the church officials. In his sermons, Demetrius of Rostov referred to Eudoxia as "our great sovereign" and prophesied her impending return to the throne. This conservative party was shattered by Peter in 1718. During the prosecution of Tsarevich Alexei Petrovich of Russia, all the bishops who supported her were executed, and Eudoxia was transferred to a convent in Ladoga.

In 1727, her grandson Peter II ascended the Russian throne and immediately recalled her to Moscow. She returned to the former capital with a great pomp and was allowed to keep her own court at the Novodevichy Convent until her death in 1731.